TAP CHi KHOA HOC VA C O N G NGHE

Tap 47, s6 2, 2009

Tr 91-100

BI^N TiNH MUN DU'A 6" NHIET 0 0 THAP LAM VAT LIEU HAP PHU, IJNG DUNG LOAI "B6 ION Cu^* TRONG NU'OC
BUI QUANG C U , T R A N MINH DIJC, T R A N THI X U A N T I N H ,

BUI QUANG MINH, DUQNG THUY DUQNG

1. MODAU Mun dira, mot loai chat thai trong ndng nghiep dugc lay tir cac ca sd san xuat xa dira d Ben Tre. Day la san pham phu tir cdng nghe san xuat gao dira, chi xa dira va dugc coi la mot loai ba thai ndng nghiep gay d nhiem dat va ngudn nude. Mdi nam, Ben Tre san xuat 50 - 60 ngan tan chi xa dira va thai ra mdi trudng khdng dudi 200 ngan tan mun dira (ti le 1/4). gay d nhiem ngudn nude va khdng khi. Tren the gidi, trong nhung nam gan day cd nhieu tac gia da nghien ciru ve thanh phan hda hgc [1, 2] va chiing minh kha nang hap phu ciia mun dira vdi cac ion kim loai nang va cac chat hiru CO. Tuy nhien, d Viet Nam chua tac gia nao nghien ciru va phat trien loai vat lieu nay vao xir li nude thai. Ngudi ta chi sii' dung mun dira de lam gia the trong hoa. san xuat dat sach. va sir dung de trong nam bao ngu... Trong bai bao nay chimg tdi trinh bay qua trinh xir li mun dira bang phuang phap hda hgc vdi axit sulfuric vdi cac dieu kien thdi gian boat hda. nhiet do boat hda. ti le vat lieu va axit khac nhau va irng dung loai bd ion Cu'' trong nude. 2. THUC NGHIEM 2.1. Hda chat HjSOj d (TQ), B a d : (10%), KMn04(5%). NaHCO, (0,1%), HNO, (TQ). NaOH (TQ), HCl, HjO cit, nude ndng, dung djch CUSO4 1000 ppm, gily quy, Na2CQ3 chuan. 2.2. Thiet bj May do pho hap thu nguyen tir AAS: SHIMADZU 6800A. can phan tich dien tir. may khuly tir, tii sly hut chan khdng, may do pH. Id nung. 2.3. Chuan hi mau xa diia hoat hda bang axit Muc dich ciia qiia trinh boat hda nhlm lam tang boat tinh cua mun dira dap img nhu cau su dung so vdi mini dira thd. Mun dira can vdi lugng xac djnh, sau dd cho axit sunfurie dac vao de yen 2 gid va boat hda vdi thdi gian, nhiet do va ti le thich hgp trong binh kin khdng cd oxy. Sau dd, de ngudi den nhiet do phdng. rira sach bIng nude cIt. nude ndng nbiSu lln cho den khi bet ion sulphate, nude lgc

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khdng cdn ket tiia trang vdi dung djch BaCl: 10%. Mau than sau khi rua dugc phai khd ngoai khdng khi va say d (50C trong 6 gid). Mau thu dugc khi hieu RA. 2.4. Chuan bi mau than hoat hoa bang axit va trung hoa bang NaHCO3(0,lN) Mun dira dugc hgat hda nhu da neu d tren. Sau khi hgat hda rira sa bd bang nude va diing dung djch NaHCOa 0,1 N de trung hda het axit va ngam trong 2 gid, sau dd rua sach bang nude cat, phai khd ngoai khdng khi va say d (50C trong 6 gid). Mau thu dugc ki hieu RAN. Qua trinh hap phu trao ddi ion dugc khao sat tren cac yeu td nhiet do boat hda. thdi gian hoat hda, ti le mun diia va axit, thdi gian khuay, pH dung djch, ndng do dung djch. giai hap, chu ki tai sinh va xir li tren mau nude thuc te. Phan tich ndng do Cu^* trong dung djch thu dugc bang phuong phap quang phd hap thu nguyen tir tren may AAS Ki hieu mdu: RA: Mun diia boat hda vdi H2SO4 dac. RAN: Mun dira boat hda vdi H2S04dac va trung hda vdi NaHC03. 3. KET QUA VA THAO LUAN 3.1. Cac tinh chat hda li ciia than RA, RAN Dien tich be mat rieng - Dien tich be mat rieng RA: 5.01 m /g; - Dien tich be mat rieng RAN: 3,03 m'/g. Hinh SEM cua than RA vd RAN

< a

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TI

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Hinh 1. hinh SEM: a. RA Ddc tinh he mat cua than mun dira

b. RAN

Ket qua phan tich phd IR cho thay mun dira sau khi xu li cd ket qua nhu sau:

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Than RA: Xuat hien cac mui phd dac trung nhdm -COOH d budc sdng: 1709 cm-', ngoai ra con xuat hien mui hap phu a khoang 1172 c m ' , day la dac trune dao dona cua nhom sunfonic.

T^^"

2b00 200U Wavenumber err 1

Pho IR cua than RA

BRUKER

S.S
E to to c

ifffOO 2000 Wflvenumnftr rm-1

Pho IR cua than RAN Theo [3] nhdm sunfonic thudng xuat hien trong khoang budc sdng (1150 -1190 cm') va mui hap thu d khoang budc sdng 1034 c m ' chinh la miii dac trung cho dao ddng nhdm S=0 [4]. Dieu nay chirng td rang cd sir hien dien ciia nhdm -HSO3 trong cau triic ciia than RA. Than RAN: Xuat hien mui phd d budc sdng 1602 cm '. day la mui phd dac trung cho nhdm(-COO-) trong cau triic ciia than. Theo phuang phap Boehm. cac nhdm cd do axit manh tuang duong vdi carboxyl trd len cd kha nang trao ddi vdi NaHCOs, cac nhdm chirc cd do axit manh tuang duang vdi lactone trd len 93

cd kha nang trao ddi vdi Na2C03 va cac nhdm chirc cd do axit manh tuang duang vdi phenol tra len cd kha nang trao ddi vdi NaOH [6, 7]. Dung lugng trao ddi tinh dugc nhu sau: Bdng I. Dung lugng trao ddi theo phuang phap Boehm Ten mau RA RAN NaHC03 (mD H"/g) 1,76 0,72 NajCOj (mD H7g) 1,36 1,30 NaOH (mD H7g) 2,00 2.05

Tir ket qua cho thay cac mau than deu cd kha nang trao ddi vdi NaHCOa, chirng td sir hien dien ciia cac nhdm chirc cd tinh axit tuong ddi manh tren be mat ciia than. Dong thdi. ket qua djnh tinh va chup phd IR nhdm chirc SO3H cho thay cd sij' xuat hien cua nhdm chiic SO3H tren than RA. Day la nhdm chirc quyet djnh kha nang trao ddi cua than. 3.2. Anh hu-dng ciia thoi gian hoat hoa den kha nang hap phu trao doi ion Cu 2+ Bang 2. Anh hudng thai gian boat hda den dung lugng hap phu trao ddi ion Cu^* len RA. RAN sau khi hgat hda d cac thdi gian 2 gid, 4 gid. 6 gid, 8 gid. 10 gid, 12 gid, nhiet do hoat hoa 150C, ti le mun dira va axit (1 g : 5,52 g). Vdi dieu kien: Ndng do Cu^* 65,46 ppm, pH = 4,5, thdi gian khuay 60 phut, khdi lugng RA, RAN la 0.05 g /50 m Thdi gian boat hda (gid) Cs (ppm) 2 4 6 8 10 12 43,46 40,5 37,99 39,11 41,62 41,16

RA a (mg/g) 22,00 24,96 27,47 26,35 23,84 24,30 Cs (ppm) 24,96 22,00 19,20 22,75 19,96 23,10

RAN a (mg/g) 40,50 43,46 46,26 42,71 45,50 42,36

bn 'MSO

n 40 -

30 20 1 10 J
0 *

1 i
ii

i
t

1
10

Thffi gian (h) Hinh 2. Anh huong ciia thdi gian boat hoa den kha nang hap phu trao doi ion Cu"

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Tir bang ket qua cho thay dung lugng hap phu theo thdi gian khdng deu nhau. va cao nhit la boat hda d 6 gid. Dieu nay li giai la do d thdi gian dau 2 gid. 4 gid qua trinh chua dii thdi gian de qua trinh dehydrat xay ra hoan toan ma chi mdi bat dau. 0 khoang thdi gian 6 gid qua trinh mat nude tinh the, cau true va dehydrat da xong. Ddng thdi d khoang thdi gian 6 gid lugng nhdm chirc cd do axit manh tuong duang nhdm caeboxyl la nhieu nhat. 3.3. Anh hu'ong cua nhiet do hoat hoa den kha nang hap phu trao doi ion Cu^"^ Bang 3. Anh hudng nhiet do boat hda den dung lugng hap phu trao doi ion Cu^'len than RA. RAN sau khi hgat hda d cac nhiet do boat hda 50C, 80C, 100C, 150C. 200C. thdi gian boat hoa 6 gid, ti le mun dira va axit(l g: 5,5 g). Vdi dieu kien: Nong do Cu"' 67ppm. Ph = 4.5. thdi gian khuay 60 phut, khdi lugng RA. RAN la 0.05 g / 50 ml

Nhiet do hoat hoa (C) 50 80 100 150 200

RA Cs (ppm) 43,80 40,04 40,10 38,20 37,80 a (mg/g) 23,20 26,96 26,90 28,80 29,20 Cs (ppm) 26,75 22,32 21.87 20,34 19.72

RAN a (mg/g) 40.25 44.68 45.12 46.66 47.28

Hinh 3. Anh huong cua nhiet do hoat hoa dSn kha nang hap phu trao doi ion Cu"* Trong khoang tir 50 - 150C nhiet do hgat hda tang thi dung lugng hap phu tang, nhung trong khi nhiet do tang tir I50"C den 200''C thi dung lugng hip phu thay ddi khdng dang ke. Dung lugng hip phu tang d nhiet do cao la do lugng nhdm chirc carboxyl sinh ra nhieu khi nung nhiet do cang cao. Va nhdm chuc carboxyl la nhdm quyk djnh kha nang hap phu trao ddi cua viit lieu [8]. 3.4. Anh hu-dng cua ti le mun dira va axit H2SO4 den kha nang hap phu trao doi ion Cu *

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Bdng 4. Anh hudng ti le mun dira va axit H2SO4 den dung lugng hap phu trao ddi ion Cu"' len than RA, RAN boat hda d 150C, 6 gid ti le mun dira va axit (1 g : 7,4 g)dugc khao sat trong dieu kien: Ndng do ion Cu'" 71 ppm, pH = 4,5 , khdi lugng RA. RAN la 0.05 g / 50 m. khuay 60 phiit Ti le mun dira va axit (g/g) 1 3,7 I 5,5 1 7,4 1 9,2 RA Cs (ppm) 44,22 41,70 40,95 40,72 a (mg/g) 26,78 29,30 30,05 30,28 Cs (ppm) 27.43 24,17 23,05 22,59 RAN a (mg/g) 43.57 46,83 47.95 48,41

1/3.7

1/5.5 1/7.4 1/9.2 Ty if (g)

Hinh 4. Anh hudng ciia ti le mun dira va axit den kha nang hap phu trao doi ion Cu"* Thuc nghiem cho thay ti le mun dira va axit la (1 g : 1,8 g) khdng du de tam deu mun dira, khi ti le mun diia va axit tang tir (1 g: 3,7 g den 1 g: 9,2 g) thi dung lugng hap phu tang, tuy nhien ti le mun dira va axit trong khoang tir (1 g: 7.4g - Ig: 9,2g) thi dung lugng hap phu hau nhu khdng tang nira. Dieu nay li giai do lugng nhdm chuc axit ton tai tren be mat than cang nhieu khi lugng axit cang tang. 3.5. Anh hu-dng cua thoi gian khuay den dung lu-ffng hap phu trao doi ion Cu * Bdng 5. Anh hudng cua thdi gian khuay den dung lugng hap phu trao ddi ion Cu ' len than mun diia RA va RAN boat hda d 150C, 6 gid, ti le mun dira va axit (1 g : 7.4 g) dugc khao sat trong d\k\ kien: Nong do ion Cu'* 68,6 ppm, pH = 4,5, khdi lugng RA, RAN la 0,05 g / 50 ml. Thdi gian khuay thay ddi tir 5 ^ 60 phut Thoi gian (phut) 5 10 15 30 45 60 RA Cs (ppm) 46,07 42,56 40,08 39,84 39,50 39,52 a (mg/g) . 22,53 26,04 28,52 28,76 29,10 29,08 Cs (ppm) 28,23 23,53 20,20 18,92 17,34 17,33 RAN a (mg/g) 40,37 45,07 48,40 49,68 51,26 51,27

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Ket qua cho thay. khi thdi gian khuay tang thi dung lugng hap phu tang, va can bang hap phu dat dugc ddi vdi than RA la 30 phut va doi vdi than RAN la 45 phiit. 3.6. Anh hu'ong cua pH den kha nang hap phu trao doi ion Cu^* Bang 6. Anh hudng ciia pH den dung lugng hap phu trao ddi ion Cu^* len than RA va RAN boat hda d 150"C. 6 gid, ti le mun diia va axit (1 g : 7,36 g) dugc khao sat trong dieu kien: Nong do ion Cu'" 69 ppm. khdi lugng RA, RAN la 0,05 g / 50 ml. Thdi gian khuly 60 phiit, pH dung djch thay ddi tir 2,07; 3,07; 4.07; 4,95; 5.5 bIng dung djch NaOH (0,1 N)vaHCl(0.1 N)" RA pH 2,07 3.07 4.07 4.95 5,55 Csau (ppm) 52,6 41,0 39,5 39,2 39,1 a (mg/g) 16.45 28.05 29.55 29.85 29,9 a (mD/g) 0,52 0,90 0.94 0,95 0,95 mDH*/g than 0,60 0,89 0,94 0,92 0,93 RAN Csau a mDH*/g mDNa*/g a than (ppm) (mg/g) (mD/g) than 0,90 0,35 1.28 28,63 40,37 1-05 20.67 48,33 0.48 1.53 1.04 0.57 18.06 50.94 1.62 1.64 0.58 1.06 17,25 51,75 1.64 0.60 1.05 17,20 51,80

Trong viing pH tir 2 den 5 thi dung lugng hap phu tang khi pH tang, khi tang pH len 5.5 thi dung luong hap phu gan nhu can bang. Nguyen nhan anh hudng cua pH den qua trinh hap phu Cu^* tren than RA, RAN dugc giai thich: Trong mdi trudng axit pH tir 2 den 2.5 dong tdn tai chu yeu ion Cu'* va ndng do H* cao hon ndng do ion Cu"* trong dung djch. do dd. cd su canh tranh giira ion H* va Cu'* trong qua trinh hap phu trao ddi dan den dung lugng hap phu thap. Trong khoang pH tii' 4 din 5.5 cd 2 dang ion (Cu^', CuOH*) tdn tai trong dung djch nen dung lugng hip phu Idn, cdn trong khoang pH tii' 5,5 den 7 da xuat hien ket tiia Cu(0H)2 [9]. 3.7. Khao sat hap phu trao doi ion Cu d cac nong do khac nhau

Bang 7. Hip phu trao ddi ion Cu'* d cac ndng do 17.8 ppm. 36.6 ppm. 69 ppm. 101 ppm. 137 ppm, 1 82 ppm tren than RA. RAN trong dilu kien: Khoi lugng RA. RAN la 0.05 g/ 50 ml. thdi gian khuly 60 phiit, pH dung djch 4.54 Ten mau Co (ppm) 17.8 36,6 RA 69,0 101,0 137,0 182,0 36,6 53,8 RAN 69,0 101,0 137,0 182.0 Csau (ppm) 1,53 12.2 39,8 73,1 106,2 151,6 0,74 9,3 17,5 44,6 80.0 125.0 a (mD/g) 0,52 0,77 0,93 0,89 0,98 0,96 1,14 1.41 1,63 1,79 1.81 1.81 pH ban dau 4,54 4.54 4,54 4,54 4,54 4.54 4.6 4.54 4.54 4.48 4.54 4.50 pH can bang 3.27 3,10 3,03 3,04 3,00 2,99 3,37 3,35 3,22 3,20 3.15 3.12 mDH /g than 0.51 0.77 0.90 0..93 0..97 0.99 0.40 0.42 0.57 0,6 0,67 0.73 0,73 1,04 1,06 1.19 1.12 1.10 97 inDNa/g than

Tir bang 7 cho thay trong qua trinh hap phu tren than RA, RAN thi cd sir thay ddi ddng thdi cua pH dung dich va ndng do ion Na* trong dung djch tir thdi diem bat dau hap phu cho den liic can bang. Lugng ion Cu^" di vao than RA gan nhu tuang duang vdi lugng ion H~ di vao dung djch va lugng Cu'* di vao than RAN cung gan tuong duang lugng H^ va Na* vao dung dich. Do do cd the ket luan ca che hap phu chu yeu tren than RA, RAN xay ra theo ea che trao ddi ion. ngoai ra cd the nghi den kha nang tao phirc cua nhdm caeboxyl va phenol vdi ion Cu^*. 2( -R-COOH ) + Cu^' (-ROO)2Cu + 2 i r 2(-R-COS03H) + Cu^^ (-ROOS03)2Cu + 2H'' 2(-R-COONa) + Cu^' (-R-C00)2Cu + 2Na* 2(-R-COS03Na)-^ Cu^* (-R00S03)2Cu + 2Na^ Phan irng tao phuc:
cooCOO,

Cu'

2+

Cu

3.8. Kha nang giai hap va tai sinh than RA va RAN sau khi hap phu trao doi ion C ^ ^ u" Bdng 8. Qua trinh giai hap phu ion Cu^* Qua trinh giai hap dugc thuc hien trong dieu kien: Ndng do HCl tii' 0,01 N den 0,15 N, Lugng than sir dung 0,1 g RA / 50 ml HCl, 0,05 g RAN / 50 ml HCl, thdi gian khuly 60 phut
RA Nong do Cu^^can bang (ppm) 24,00 33.74 39,70 42,90 43,10 43,12 43,09 RAN Nong do Cu *can b^ng (ppm) 30,70 36,72 40,90 43,45 45,20 45,23 45,20

Nong do HCl (N) 0,010 0,025 0,050 0,075 0,100 0,125 0,150

% giai hap 55,66 78,25 92,07 99,50 99,95 100 99,93

% giai hap 68,00 81,20 90,40 96,20 100 100 100

Bdng 9. Dung lugng hap phu theo sd lan tai sinh cua than RA, RAN
So Ian tai sinh Ten mau RA RAN 1 a (mD/g) 0,684 1,6 2 a (mD/g) 0,634 0,997 3 a (mD/g) 0,5995 0,944 4 a (mD/g) 0,5997 0,9 5 a (mD/g) 0,5873 0,866

Than RA cd dung lugng hap phu giam 15% sau 5 lan tai sinh, than RAN cd dung lugng hap phu giam 50% sau 5 lan tai sinh.

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3.9. Xur li nu-dc thai thyc te Nude thai thuc te lay tir ca sd ma dien qua xir li bang vat lieu RA va RAN cho biet ham luang cac nguyen td kim loai nang nhu niken, sat, ddng, kem cd ham luong dat yeu cau thai ra ngoai theo TCVN 5945-2005 (cot B). 5dg 70. Ket qua xu li nude tai xi ma Loai than Mau nu-oc 1 Hien trang Trudc xir li Sau xir li Trudc xu li 2 Sau xir li TCVN 5945-2005 2,63 0,49 5 Fe (ppm) Zn^" (ppm) 18,6 1,40 338 2,76 3 RA Ni^^ (ppm) 4,00 0,92 18,7 0,80 0,5
/-. 2-^

RAN Fe^^ (ppm) Zn^^ (ppm) 18,6 0,78 2,63 0 5 338 1.08 3 Ni^^ (ppm) 4,00 0,14 18,7 0.54 0.5
/^

2^

Cu (ppm) 9,6 0,57 28,80 0,87 2

Cu (ppm) 9,60 0,30 28,80 0.57 2

4. KET LUAN Ket qua cho thIy mun dira BSn Tre sau khi boat hda vdi axit sunfuaric d 150"C. trong 6 gid, cd chira cac nhdm chiic -COOH, -OH, -SO3H, -COONa, -SOjNa... cd kha nang hip phu tdt ion Cu^"^ trong dung djch. Mun dira sau khi boat hda chira lugng nhdm chirc caeboxyl cao ban nguyen lieu ban dau. Viec thir nghiem hap phu vdi ion Cu cho thay: - Mun dira sau khi boat hda bIng axit H2SO4 trong diSu kien 150C. thdi gian 6 gid. ti le mun dira va axit (I g : 7,4 g) cho dung lugng hap phu 31 mg/g. - Mun diia khi boat hda bIng axit H2SO4 trong dieu kien 150C, thdi gian 6 gid, ti le mun dira va axit (1 g : 7,4 g) sau do trung hda vdi NaHCO3(0,l N) cho dung lugng hap phu 57 mg/g. Than RA, RAN hip phu tot ion Cu^* trong khoang pH dung djch tir 4 den 5,5. Ca che hip phu chu yeu cua ion Cu'* tren than RA, RAN chu ylu xay ra theo ca che hap phu - trao ddi ion. Than boat tinh sau khi hip phu cd the giai hip bang dung djch HCl. Qua thir nghiem xir li mlu nude thuc te cho thIy kk qua sau ham lugng mdt sd kim Igai xir li dat tieu chuIn thai ra mdi trudng. TAI LIEU THAM KHAO IK. Raveendran, Anuradda Ganesh, and Kartic C Khilart - Influence of mineral matter on biomass pyrolysis characteristics. Fuel Proccesing Technology 74 (12) (1995) 1813.

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C Namasivayam, M.V. Sureshkumar - Removal of ehromium(VI) from water and wastewater using surfactant modified coconut coir pith as a biosorbent, Bioresource Technology 98 (2007) 123-13. Eun Woo Shin, Roger M. Rowell - Cadmium ion sorption onto lignocellulosic biosorbent modified by sulfonation: the origin of sorption capacity improvement, Chemosphere 60 (2005)1054-1061. 4. Kelly R- Benak, Lourdes Dominguez, James Economy, and Christian L. Mangun Sulfonation of pyropolymeric fibers derived from phenol-formaldehyde resins. Carbon 40 (2002)2323-2332. Phan Nggc Hda, Nguyin Thanh Hdng - Tap chi Hda hgc 40 (4) (2002) 7-10. H.P. Boehm - Adv.Catalys. 16(1966) 179-225. , j, ^"i

J.

6. 1.

H.P.Boehm - Some aspects of the surface chemistry of carbon black and other carbon Carbon 32 (5) (1994) 759-769. Phan Nggc Hoa - Luan an Tien sT hda hgc. Nghien ciru che tao vat lieu hap phu va trao ddi ion tir sgi thien nhien de ung dung vao xir li mdi trudng, TP.HCM, 2004. Mohammed Ajmal, Akhtar Hussain Khan. Shamin Ahmad and Anees Ahmad - Role of sawdust in the removed of eopper(II) from industrial wastes, Wat. Res. 32 (10) (1998) 3085-3091. SUMMARY MODIFYING COIR PITH AT LOW TEMPERATURE AND USING FOR ADSORPTION OF ION Cu'* FROM WATER

Coir pith - a low value agriculture byproduct has been used in some manufacturing areas but not valuable. Our thesis's objective is modify coir pith by acid to get an adsorbent for removing cations from contaminated water. These achieved technical conditions are: after washed and dryed material (coir pith) has been activated with concentrated sulphuric acid (98%o) at I50C in 6 hours, coir pith/acid proportion (1 g : 7,4 g). Then, one part was washed with distilled water to remove the free acid (RA) and another part soaked in 0,1 N sodium bicarbonate solution in 2 hours to remove any residual acid (RAN). The results of study show that the oxidation of activated carbons increase the amount of surface oxygen complexes and sulfonic group also occurred in structure of activated carbon. The amount of ion Cu adsorbed is about 31 mg/g on RA and 57 mg/g on RAN. Dia chi: Bill Quang Cu, Biii Quang Minh, Vien Cdng nghe hda hgc. Tran Minh Due, Tran Thj Xuan Tinh, Vien Cdng nghe mdi trudng. Duong Thiiy Duong, Trudng Dai hgc Can Tha. Nhan hdi ngdy 12 thdng 8 nam 2008

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